KR20170072277A - Dishwasher detergent containing metal complexes - Google Patents

Abstract

상기 식에서, 각 X는 본원에서 정의한 바와 같다.The present invention has the general formula M ^{n +} L (A ^m-) _{n / m} (where M is a metal cation, A is any anion, n and m is an integer of from 1 to 6, L is for a neutral ligand of the formula II The present invention relates to an automatic dishwasher detergent containing a metal complex. The automatic dishwasher detergent has improved cleaning performance in removing burned contaminants. Also disclosed is the use of the automatic dishwasher detergent and an automatic cleaning method using the dishwasher detergent.
≪

Wherein each X is as defined herein.

Description

DISHWASHER DETERGENT CONTAINING METAL COMPLEXES <br> <br> <br> Patents - stay tuned to the technology DISHWASHER DETERGENT CONTAINING METAL COMPLEXES

The present invention relates to an automatic dishwasher detergent exhibiting improved cleaning performance upon removal of burned contaminants, the use of such dishwasher detergents, and a method of automatically cleaning a dishwasher using such dishwasher detergents.

The most important criterion for automatic dishwashing is the cleaning performance for a wide variety of contaminant types introduced into the dishwasher in the form of food residues. In the case of hard to remove contaminants, such as those occurring during the preparation of protein-containing and starchy foods at high temperatures (roasting, baking, frying, gratinizing, etc.), particularly referred to as burned contaminants, The cleaning performance is still unsatisfactory. This unsatisfactory cleaning performance leads to a lack of satisfaction from the consumer's perspective. There is therefore a general need for an automatic dishwasher detergent that exhibits good cleaning performance even for burned contaminants.

Surprisingly, it has been found that the metal complexes used according to the present invention present improved cleaning performance against burned contaminants when used in conventional dishwasher detergent formulations.

Accordingly, a first aspect of the present invention is a dishwasher detergent comprising 0.001-10.0 wt.%, Especially 0.01-1. 0 wt.% Of at least one metal complex of the formula I, based on the total weight of the dishwasher detergent, The present invention relates to a dishwasher detergent.

(I)

M ^{n +} L (A ^m- ) _{n / m}

In this formula,

M is a metal cation selected from Groups 2 to 15 of the Periodic Table of the Elements;

A is an optional anion;

n and m are integers selected from 1 to 6;

L is a neutral ligand of formula &lt; RTI ID = 0.0 &gt;

&Lt;

In this formula,

Each X is independently O or NR;

Each R is independently selected from H, unsubstituted or substituted, linear or branched C _1-20 alkyl, unsubstituted or substituted, linear or branched C _1-20 heteroalkyl, unsubstituted or substituted, linear or branched C _{2 -20} alkenyl, unsubstituted or substituted, linear or branched C _2-20 alkenyl heteroaryl, and unsubstituted or substituted, linear or are independently selected from branched C _2-20 alkynyl.

In one preferred embodiment, each R is _{H, - (CH 2) o} -CH 3 ( wherein o is an integer selected from 3 to _{13), - (CH 2) p} -COOH and - (CH _{2) p} -OH ( Wherein p is each integer selected from 1 to 6.

The invention also relates to the use of the dishwasher detergent according to the invention in an automatic dishwashing method, in particular for the purpose of improving the washing performance in automatic dishwashing machines.

In addition, the present invention relates to a dishwasher detergent method in accordance with the present invention, particularly for the purpose of improving the cleaning performance.

Finally, the invention relates to the use of the metal complexes used according to the invention to improve the cleaning performance of automatic dishwasher detergents.

These and further aspects, features and advantages of the present invention will become apparent to those of ordinary skill in the art upon review of the following detailed description and claims. All of the features from one aspect of the invention can be used in another aspect of the invention. Moreover, it should be understood that the embodiments contained herein are intended to illustrate and exemplify the invention, but need not necessarily limit the invention, and in particular the invention is not limited to these embodiments. All percent information is percent by weight unless otherwise indicated. The numerical ranges in the form "x to y" include the values mentioned. It is needless to say that when some preferred numerical ranges are expressed in this form, all ranges generated from combinations of different end points are similarly encompassed.

As used herein, "at least one" means one or more, which refers to one, two, three, four, five, six, seven, eight, nine, or more. For a constituent, the expression refers to the type of constituent and does not refer to the absolute number of molecules. Thus, "at least one metal complex" means, for example, at least one type of metal complex, i.e. one type of metal complex or a mixture of several different metal complexes may be mentioned together with weight information, Refers to all compounds of the described type that are present in the composition / mixture, i.e., the composition does not include any additional compounds of this type beyond the indicated amount of the corresponding compound.

All percentages provided in connection with the compositions described herein, unless otherwise expressly indicated, refer to weight percentages, based on the subject mixture, in each case.

Within the scope of the present invention, unless otherwise indicated, fatty acids or fatty alcohols or derivatives thereof preferably represent branched or unbranched carboxylic acids or alcohols or derivatives thereof containing from 6 to 22 carbon atoms. In particular, it is also possible to correspondingly use oxoalcohols or derivatives thereof obtainable according to the oxo synthesis of, for example, Roelen.

Whenever an alkaline earth metal is mentioned later as a counter ion to a monovalent anion, this will also mean that only the alkaline earth metal is present, of course, only half of the material, sufficient for charge equalization as an anion.

The metal complexes used in the formulations according to the invention are metal complexes of the general formula (I)

(I)

M ^{n +} L (A ^m- ) _{n / m}

In these metal complexes, M is a metal of Groups 2 to 15 of the Periodic Table of the Elements (IIA, IIIA, IVA, VA, IIIB, IVB, VB, VIB, VIIB, VIIIB, IB, IIB CAS or 2-5 groups, ). &Lt; / RTI &gt; In various embodiments, M is selected from the group consisting of Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Sr, Y, Zr, Pd, Ag, In, Sn, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb and Bi. In a further embodiment, the metal is selected from divalent and trivalent metal cations, especially those mentioned above. In yet a further embodiment, the metal is Cu, Zn, Co, Cr, Ni, Fe, Ru, Rh, Mn, Bi, in particular Cu, Zn, Co, Ni, Fe, Mn and Bi, more preferably Cu ^{2 +,} Zn ^2+, Fe ^{+ 2,} Fe ^{+ 3,} Co ^{+ 2,} Co ^{+ 3,} Mn ^{+ 2,} Mn ^{+ 3} and Bi ^{+ 3,} even more preferably Cu ^{2 +,} Zn ^{2 +} or Bi ³⁺ , Most preferably Cu ²⁺ or Zn ²⁺ , especially Zn ²⁺ .

n represents the valence of the metal cation and is an integer from 1 to 6, preferably from 1 to 5, in particular from 2 or 3.

A is, in particular, inorganic anions such as ^{F -, Cl -, Br -} , I -, OH -, HSO 3 -, SO 3 2-, SO 4 2-, HSO 4 -, NO 2 -, NO 3 -, PO _{^{4 3-, HPO 4 2 -,}} H 2 PO 4 -, BF 4 -, PF 6 - and ClO ₄ ^-, or an organic anion, such as acetate, citrate, formate, glutarate, lactate, maleate, Is an optional anion selected from the group consisting of malonate, oxalate, pyruvate, tartrate, methanesulfonate (mesylate), methylsulfate, tosylate, and succinate.

L is a neutral ligand of formula (II).

&Lt;

In this formula,

X is O or NR.

In different embodiments, all X is O or all X is NR.

Each R is independently selected from the group consisting of H, unsubstituted or substituted, linear or branched C _1-20 alkyl, preferably linear C _8-18 alkyl, unsubstituted or substituted, linear or branched C _1-20 heteroalkyl, Unsubstituted or substituted, linear or branched C _2-20 alkenyl, unsubstituted or substituted, linear or branched C _2-20 heteroalkenyl, and unsubstituted &lt; RTI ID = 0.0 & Or a substituted, linear or branched C _2-20 alkynyl.

Preferably, each R is _{H, - (CH 2) o} -CH 3 ( wherein o is an integer selected from 3 to _{13), - (CH 2)} p -COOH and - (CH _{2) p} -OH (wherein p Are each independently selected from 1 to 6).

In various embodiments of the present invention, at least one R is - (CH ₂ ) _o -CH ₃ , wherein o is an integer selected from 5 to 9, especially 7.

In various embodiments of the invention, at least one X, preferably all X is NR. In such embodiments, at least one R is H, and, preferably from 2 to 3 and R is H, and at least one R, and preferably exactly one R is - and (CH _{2) o} -CH _3, where o is an integer selected from 5 to 9, especially o is 7;

In one embodiment, the ligand of formula (II) is an N-substituted cyclene (1,4,7,10-tetraazacyclododecane), especially N-mono-C _4-14 -alkylcycloylene, preferably N _-Mono -C _6-10 -alkylcyclo, more preferably N-mono-octylcyclen. In this embodiment, the metal cation is preferably Zn ^{2 +} and the anion is preferably SO ₄ ^2- .

In various embodiments of the invention, at least one X, preferably all X is NR. In this embodiment, at least one R is H, preferably 2 to 3 R are H, and at least one R, preferably exactly one, R is an alkyl functional group as defined above, such as octyl, decyl, Dodecyl, tetradecyl or hexadecyl functional group. In one embodiment, the ligand of formula II is selected from the group consisting of N-substituted cyclohexane (1,4,7,10-tetraazacyclododecane), especially N-mono-alkylcyclene, preferably N-mono- N-mono-decylcyclene, N-mono-dodecylcyclen, N-mono-tetradecylcyclen or N-mono-hexadecylcyclen. In such embodiments, the metal cation is preferably a Cu ^{2 +,} Zn ^{2 + 3} or Bi ^+, and particularly preferably Cu ^{2 +} or Zn ^{2 +,} especially Zn ^{2 +.} In such embodiments, the anion may also be a sulfate anion.

The formulations according to the invention are characterized in that they contain 0.001 to 10% by weight, preferably 0.01 to 1% by weight, more preferably approximately 0.1 to 1% by weight, based on the total weight of the dishwashing detergent, . The absolute amount is typically in the range of 0.01 to 0.2 g / operation, preferably in the range of 0.05 to 0.2 g / operation.

"Approximately" or "about," as used herein in reference to a numerical value, refers to a numerical value +/- 10%, preferably +/- 5%.

The formulations according to the invention can also be used in combination with surface active agents, in particular nonionic surfactants and / or anionic surfactants, builders, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular protective agents, , At least one, preferably at least two additional components, preferably selected from the group consisting of antiseptics, antimicrobial active ingredients and disintegration adjuvants.

The formulations described herein preferably include at least one nonionic surfactant. As the nonionic surfactant, all nonionic surfactants known to those of ordinary skill in the art can be used.

Suitable non-ionic surfactants are, for example, alkylglycosides of the formula RO (G) _x wherein R is a methyl-branched in the primary straight or methyl-branched, especially 2- Corresponding to an aliphatic functional group having from 1 to 12 carbon atoms, preferably from 12 to 18 carbon atoms, and G is a glycose unit having 5 or 6 carbon atoms, preferably a glucose. The degree of oligomerization x indicating the distribution of monoglycosides and oligoglycosides is an arbitrary number from 1 to 10; x is preferably 1.2 to 1.4.

N-cocoalkyl-N, N-dimethylamine oxide and N-tallowyl-N, N-dihydroxyethylamine oxide, and fatty acid alkanolamide types of amine oxide type nonionic surfactants, Of non-ionic surfactants may also be suitable. The amount of such nonionic surfactant is preferably less than or equal to the amount of ethoxylated fatty alcohol, especially less than half of the ethoxylated fatty alcohol.

A further suitable surfactant is a polyhydroxy fatty acid amide, also known as PHFA.

Preferably, however, low-foam forming nonionic surfactants, especially alkoxylated, especially ethoxylated, low-foam forming nonionic surfactants, are used. It is particularly preferred when the automatic dishwasher detergent comprises a nonionic surfactant from the group of alkoxylated alcohols.

One class of non-ionic surfactants that can be used is an alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl ester, preferably comprising from 1 to 4 carbon atoms in the alkyl chain, May be used as nonionic surfactants or in combination with other nonionic surfactants.

Surfactants that should preferably be used include ethoxylated primary alcohols and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) Origin. These (PO / EO / PO) nonionic surfactants are characterized by good foam control.

Nonionic surfactants including alternating ethylene oxide and alkylene oxide units may be preferred. Among these, as a result, a surfactant comprising an EO-AO-EO-AO block is preferred, in which in each case from 1 to 10 EO or AO groups are bonded together, followed by blocks from each other group. Here, nonionic surfactants represented by the following formulas are preferable,

Wherein R ¹ represents a linear or branched, saturated, monounsaturated or polyunsaturated C _6-24 alkyl functional group or an alkenyl residue, each group R ² and R ³ independently of one another are -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ , and the subscripts w, x, y and z independently of one another represent integers from 1 to 6.

Thus, in particular, it is preferred to use one or more ethylene oxide units, then one to four propylene oxide units, then one to four ethylene oxide units, then a _C9-15 alkyl functional group having one to four propylene oxide units Lt; / RTI &gt; surfactants are preferred.

Preferred nonionic surfactants are therefore those of the formula &lt; RTI ID = 0.0 &gt;

_{^{R 1 -CH (OH) CH 2}} O- (AO) w - (A'O) x - (A "O) y - (A"'O) z -R 2

In this formula,

R ¹ represents a linear or branched, saturated, monounsaturated or polyunsaturated C _6-24 alkyl functional group or alkenyl residue;

R ² represents H or represents a linear or branched hydrocarbon functional group having from 2 to 26 carbon atoms;

- A, A ', A "and A"' independently of one another are -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH _{2 -CH 2, -CH 2 -CH (CH} 3) -CH 2 -, -CH 2 -CH (CH 2 -CH 3) represents a functional group from the group consisting of;

- w, x, y and z represent values of from 0.5 to 120, where x, y and / or z may also be zero.

In particular, the formula ^{_{R 1 O [CH 2 CH 2}} O] x CH 2 CH (OH) in accordance with R ^2, having from 2 to 30 carbon atoms, preferably a linear or branched having from 4 to 22 carbon atoms, saturated or unsaturated, aliphatic, or in addition to the functional group R ¹ represents an aromatic hydrocarbon functional group, a linear or branched, saturated or unsaturated aliphatic or an aromatic hydrocarbon functional group R ² also, and the expression has 1 to 30 carbon atoms, x is 1, Terminally capped poly (oxyalkylated) nonionic surfactant, which has a value of from 0 to 90, preferably from 30 to 80, in particular from 30 to 60, is preferred.

Surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² are particularly preferred, wherein R ¹ is a 4- to 18- R ² represents a linear or branched hydrocarbon functional group having 2 to 26 carbon atoms or a mixture thereof, x represents a value of 0.5 to 1.5, and R ² represents a linear or branched hydrocarbon functional group having 2 to 26 carbon atoms or a mixture thereof, y represents a value of at least 15.

These groups of nonionic surfactants are, for example, C _2-26 fatty alcohol- (PO) ₁ - (EO) _15-40 -2-hydroxyalkyl ethers, especially also C _8-10 fatty alcohol- (PO) ₁ includes a (EO) ₂₂ -2- hydroxy-decyl ether. In addition, the formula ^{_{R 1 O [CH 2 CH 2}} O] x [CH 2 CH (R 3) O] y CH 2 CH (OH) those ends of the R ² - capped poly (oxyalkylation) is particularly preferably a nonionic surfactant Wherein R ¹ and R ² independently of one another represent a linear or branched, saturated, monounsaturated or polyunsaturated hydrocarbon functional group having from 2 to 26 carbon atoms and R ³ independently of one another are -CH ₃ , CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , preferably -CH ₃ , x and y independently of one another represent a value of from 1 to 32, ³ = -CH ₃ and x a non-ionic surfactant with a value of 15 to 32 and the value for y 0.5 to 1.5 for the very particularly preferred.

Preferably more nonionic surfactants that can be used has the formula _{^{R 1 O [CH 2 CH (}} R 3) O] x [CH 2] k CH (OH) [CH 2] the terminal of the _j OR ² - capped poly ( Oxyalkylated) nonionic surfactant wherein R ¹ and R ² represent a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functional group having from 1 to 30 carbon atoms, R ³ represents H or Butyl or 2-methyl-2-butyl functional groups, x represents a value of from 1 to 30, k and j represent a number of from 1 to 12, Preferably a value of 1 to 5. [ Value x ≥ 2 in the case the general formula _{^{R 1 O [CH 2 CH (}} R 3) O] x [CH 2] k CH (OH) [CH 2] , each R ³ in the _j OR ² may be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functional groups having from 6 to 22 carbon atoms, with functional groups having from 8 to 18 carbon atoms being particularly preferred. H, CH ₃ or -CH ₂ CH ₃ is particularly preferred for the functional group R ³ . Particularly preferred values for x range from 1 to 20, in particular from 6 to 15.

As described above, each R &lt; ³ &gt; in the above formula may be different when x &gt; = 2. In this way, the alkylene oxide units in the angle brackets may be different. For example, if x is 3 then the functional group R ³ can be selected to form an ethylene oxide- (R ³ = H) or propylene oxide- (R ³ = CH ₃ ) unit, (EO) (PO) (PO) (EO) (PO) (EO), (EO) PO) (EO) and (PO) (PO) (PO). The value 3 for x is selected here for example and may also be obviously larger, where the range of variation increases as the value of x increases, for example a large number of (EO) groups with a small number of (PO) groups Includes combinations, or vice versa.

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, whereby said formula is R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH OH) CH ₂ OR ² . In the last formula, R ¹ , R ² and R ³ are as defined above and x represents a number from 1 to 30, preferably from 1 to 20, in particular from 6 to 18. Surfactants in which the functional groups R &lt; ¹ &gt; and R &lt; ² &gt; contain from 9 to 14 carbon atoms, R &lt; ³ &gt; represents H and x has a value of from 6 to 15 are particularly preferred.

Finally, nonionic surfactants which have proved to be particularly effective are those of the formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ² ,

R ¹ represents a linear or branched, saturated, monounsaturated or polyunsaturated C _6-24 alkyl functional group or alkenyl residue;

R ² represents a linear or branched hydrocarbon functional group having from 2 to 26 carbon atoms;

- A represents a functional group from the group consisting of CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ and CH ₂ CH (CH ₃ ), preferably CH ₂ CH ₂ ,

w represents a value of from 1 to 120, preferably from 10 to 80, in particular from 20 to 40;

This group of nonionic surfactants is, for example, C _4-22 fatty alcohol- (EO) _10-80 -2-hydroxyalkyl ethers, especially C _8-12 fatty alcohol- (EO) ₂₂ -2-hydro include (EO) _40-80 -2- hydroxyalkyl ether-hydroxy-decyl ether, and C _4-22 fatty alcohol.

In various embodiments of the present invention, it is also possible to use the corresponding end-capped hydroxy mixed ether instead of the above-defined end-capped hydroxy mixed ether. Wherein R ² is hydrogen and R ¹ , R ³ , A, A ', A ", A"', w, x, y and z are as defined above.

In a different embodiment, the formulations described herein, comprising a non-ionic surfactant from the group of at least one non-ionic surfactant, preferably a hydroxy mixed ether, are prepared by mixing the surfactant with at least one non- 2% by weight, preferably at least 5% by weight. The absolute amount used per application may range, for example, from 0.5 to 10 g / operation, preferably from 1 to 5 g / operation.

All anionic surface-active materials are suitable anionic surfactants in dishwasher detergents. These are characterized by water-soluble anionic groups such as carboxylate, sulfate, sulfonate or phosphate groups and lipophilic alkyl groups having approximately 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, esters, ether and amide groups and hydroxyl groups may be present in the molecule. Suitable anionic surfactants are preferably present in the form of sodium, potassium and ammonium salts, and monoalkanols, dialkanols and trialkanolammonium salts having 2 to 4 carbon atoms in the alkanol group.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and having up to 12 glycol ether groups in the molecule.

In various embodiments, the dishwasher detergent thus comprises at least one surfactant of the formula R ⁴ -O- (AO) _n -SO ₃ -X ⁺ .

In this formula, R ⁴ represents a linear or branched, substituted or unsubstituted alkyl, aryl or alkyl-aryl functional group, preferably a linear, unsubstituted alkyl functional group, particularly preferably a fatty alcohol functional group. Preferred functional groups R ¹ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl functional groups and mixtures thereof, wherein even carbon atoms Is preferable. Particularly preferred functional groups R ¹ are derived from C ₁₂ to C ₁₈ fatty alcohols, such as coconut fatty alcohols, tallow fatty alcohols, lauryl, myristyl, cetyl or stearyl alcohols, or C ₁₀ to C ₂₀ oxoalcohols.

AO represents ethylene oxide (EO) or propylene oxide (PO) grouping, preferably ethylene oxide grouping. The subscript n represents an integer of 1 to 50, preferably 1 to 20, in particular 2 to 10. n is very particularly preferred when n represents the number 2, 3, 4, 5, 6, 7, or 8. X represents a monovalent cation or n represents an n-th portion of the cation, preferably an alkali metal ion, and among these Na ⁺ or K ⁺ , Na ⁺ is extremely preferable. Additional cations X ⁺ may be selected from _{^{NH 4 +, 1/2 Zn 2 +}} , 1/2 Ca 2 +, 1/2 Mn 2 + , and mixtures thereof.

Particularly preferred anionic surfactants are selected from fatty alcohol ether sulfates of formula (A-1).

&Lt; Formula (A-1) >

Wherein k = 11 to 19 and n = 2, 3, 4, 5, 6, 7 or 8. A very particularly preferred representative is Na- _C12-14 fatty alcohol ether sulfate (k = 11-13, n = 2 in formula A-1) comprising two EO.

Additionally or alternatively, the agent may also comprise at least one surfactant of the formula R ⁵ -A-SO ₃ -Y ⁺ .

In this formula, R ⁵ represents a linear or branched, substituted or unsubstituted alkyl, aryl or alkyl-aryl functional group, and grouping -A- represents -O- or a chemical bond. In other words, sulfate-(A = O) or sulfonate- (A = chemical bond) surfactants can be described using the formulas described above. Depending on the choice of grouping A, certain functional groups R &lt; ⁵ &gt; are preferred. In the sulfate surfactant (A = O), R &lt; ⁵ &gt; is preferably a linear, unsubstituted alkyl functional group, particularly preferably a fatty alcohol functional group. Preferred functional groups R ⁵ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl functional groups and mixtures thereof, wherein even carbon atoms Is preferable. Particularly preferred functional groups R ⁵ are derived from C ₁₂ to C ₁₈ fatty alcohols, such as coconut fatty alcohols, tallow fatty alcohols, lauryl, myristyl, cetyl or stearyl alcohols, or C ₁₀ to C ₂₀ oxoalcohols. Y represents a monovalent cation or n represents an n-th portion of a cation, preferably an alkali metal ion, and among these Na ⁺ or K ⁺ , Na ⁺ is extremely preferable. Additional cation Y ⁺ of a can be selected from _{^{NH 4 +, 1/2 Zn 2 +}} , 1/2 Mg 2 +, 1/2 Ca 2 +, 1/2 Mn 2 +, and mixtures thereof.

Such particularly preferred surfactants are selected from fatty alcohol sulfates of the formula:

In the above formula, k = 11 to 19. A very particularly preferred representative is Na-C _12-14 fatty alcohol sulfate (k = 11-13).

In a sulfonate surfactant (A = chemical bond), R &lt; ⁵ &gt; is preferably a linear or branched unsubstituted alkyl-aryl functional group. X represents a monovalent cation or n represents an n-th portion of a cation, and is preferably an alkali metal ion, and among these Na ⁺ or K ⁺ , Na ⁺ is extremely preferable. Additional cations X ⁺ may be selected from _{^{NH 4 +, 1/2 Zn 2 +}} , 1/2 Mg 2 +, 1/2 Ca 2 +, 1/2 Mn 2 +, and mixtures thereof. These surfactants can be selected from linear or branched alkyl benzene sulfonates.

Cationic and / or amphoteric surfactants such as betaine or quaternary ammonium compounds may also be used in place of or in conjunction with the surfactants described. However, it is preferred not to use cationic and / or amphoteric surfactants.

Builders that may be present in dishwasher detergents include, in particular, silicates, aluminum silicates (especially zeolites), carbonates, organic dicarboxylic acids and polycarboxylic acids, and aminocarboxylic acids and their salts, and their use In the absence of ecological biases, there are also phosphates. Naturally, a mixture of such materials can also be used.

For example, it is possible to use crystalline phyllosilicates of the formula NaMSi _x O _{2 x +1} y H ₂ O, wherein M is sodium or hydrogen and x is 1.9 to 22, preferably 1.9 to 4 Wherein a particularly preferred value for x is 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. [ Crystalline phyllosilicates of the formula NaMSi _x O _{2 x +1} y H ₂ O are commercially available, for example, under the trade name Na-SKS by Clariant GmbH (Germany). Examples of such silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyait), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, , the _{Na-SKS-3 (Na 2} Si 8 O 17 and H ₂ O x) or _{Na-SKS-4 (Na 2} Si 4 O 9 and H ₂ O x, tight marker). For the purposes of the present invention, crystalline phyllosilicates of the formula NaMSi _x O _{2 x +1} y H ₂ O, wherein x represents 2, are particularly suitable. Particularly, all of? - and? - sodium silicate Na ₂ Si ₂ O ₅ .y H ₂ O are preferred, and especially Na- SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 -Na ₂ Si ₂ O _5, room lights) to sodium, Na-SKS-9 (NaHSi 2 O 5 and _{H 2 O), Na-SKS} -10 (NaHSi 2 O 5 H ₂ O and 3, Kane mite), Na-SKS-11 (t-Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ) are preferable.

Automatic dishwasher detergent, 0.1 to 20% by weight, based on the total weight of these formulations in each case, preferably 0.2 to 15% by weight, especially 0.4 formula of to 10% by weight NaMSi _x O _{2x + 1} and y H ₂ O &lt; / RTI &gt; of the crystalline &lt; RTI ID = 0.0 &gt; phyllosilicate. &Lt; / RTI &gt;

It is also possible to use amorphous sodium silicates with Na ₂ O: SiO ₂ modules of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8, especially 1: 2 to 1: 2.6, And exhibit delayed dissolution and secondary washing properties. Delayed dissolution compared to conventional amorphous sodium silicates may have been effected in a variety of ways, for example by surface treatment, compounding, compaction / compression or over-drying. Within the scope of the present invention, the term "amorphous" means that the silicate does not provide any sharp X-ray reflections in X-ray diffraction experiments, such as the typical sharp X-ray reflections in crystalline materials, Of the scattered X-rays having a width of at least one of the scattered X-rays.

Within the scope of the invention, such silicates or their silicates, preferably alkali silicates, particularly preferably crystalline or amorphous alkaline disilicates, are in each case in the range of from 1 to 40% by weight, based on the weight of the automatic dishwashing detergent, It is preferably present in the formulation in an amount of 2 to 35% by weight.

Of course, it is also generally possible to use known phosphates as builder materials, provided that such use is not avoided for ecological reasons. Of the plurality of commercially available phosphates, alkali metal phosphates have the greatest significance in the laundry or dishwasher detergent industry, with pentasodium and pentapotassium triphosphate (sodium or potassium tripolyphosphate) being particularly preferred.

Alkali metal phosphate is a term encompassing all alkali metal (especially sodium and potassium) salts of different phosphates wherein, in addition to the higher molecular weight representatives, a distinction is made between metaphosphoric acid (HPO ₃ ) _n and orthophosphoric acid H ₃ PO ₄ . Phosphates combine several advantages: they act as an alkali carrier and prevent lime scaling on lime scale deposits or woven fabrics on mechanical parts and additionally contribute to cleaning performance.

Technically particularly important phosphates include pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), and the corresponding potassium salts pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate) and the corresponding mixed salts Sodium &lt; / RTI &gt; potassium tripolyphosphate). Preferably, however, the formulation is phosphate-free.

Within the scope of the present application, when phosphates are used as materials having a cleansing action in an automatic dishwasher detergent, the preferred formulations comprise such phosphates or their phosphates, preferably alkali metal phosphate (s), particularly preferably penta Sodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) is added in each case in an amount of from 5 to 80% by weight, preferably from 10 to 60% by weight, in particular from 18 to 45% by weight, based on the weight of the automatic dishwashing detergent .

Dishwasher detergents may also include phosphonates, especially as additional builders. The phosphonate compound used is preferably a hydroxyalkane phosphonate and / or an aminoalkane phosphonate. Of the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Possible preferred aminoalkanephosphonates include ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepenta methylenephosphonate (DTPMP) and its higher homologues. The phosphonate is present in the formulation in an amount of preferably from 0.1 to 10% by weight, in particular from 0.5 to 8% by weight, in each case based on the total weight of the dishwashing detergent.

Other builders are alkali carriers. For example, mixtures of alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, alkali silicates, alkali metal silicates and mixtures of the above-mentioned materials are contemplated Alkali carriers, in which alkali carbonates, especially sodium carbonate, sodium hydrogencarbonate or sodium sesqui carbonate, can be used in the meaning of the present invention. A builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred. Tripolyphosphate and a builder system containing a mixture of sodium carbonate and sodium silicate are likewise particularly preferred. In view of the low chemical compatibility with the remaining constituents of the automatic dishwasher detergent relative to other builder materials, the optional alkaline metal hydroxides may in each case be used in only a small amount, preferably in a small amount based on the total weight of the automatic dishwashing detergent Is preferably used in an amount of less than 10% by weight, especially less than 6% by weight, particularly preferably less than 4% by weight, especially less than 2% by weight. Particular preference is given to preparations which contain less than 0.5% by weight of alkali metal hydroxides, in particular those which do not contain alkali metal hydroxides, based on the total weight of the preparation.

The carbonate (s) and / or the hydrogen carbonate (s), preferably the alkaline carbonate (s), particularly preferably the sodium carbonate, are used in each case based on the weight of the automatic dishwashing detergent In an amount of from 2 to 50% by weight, preferably from 5 to 40% by weight, particularly preferably from 7.5 to 30% by weight. (S) and / or hydrogencarbonate (s) of less than 20% by weight, in particular less than 17% by weight, preferably less than 13% by weight and especially less than 9% by weight, based on the weight of the automatic dishwashing agent, , Preferably an alkaline carbonate (s), particularly preferably a formulation containing sodium carbonate is particularly preferred.

In particular, polycarboxylate / polycarboxylic acid, polymer polycarboxylate, aspartic acid, polyacetal, dextrin, additional organic kos builders and phosphonates, which have already been mentioned above as builders, will be referred to as organic builders . These classes of substances are described below.

The organic builder materials which can be used are polycarboxylic acids which can be used, for example, in the form of free acids and / or sodium salts thereof, wherein the polycarboxylic acid means such a carboxylic acid having more than one acid functional group . These include, for example, citric, adipic, succinic, glutaric, malic, tartaric, maleic, fumaric, saccharic, nitrilotriacetic (NTA) And mixtures thereof. In addition to the builder effect, the free acid is typically also an acidifying component and is therefore also used to set a lower and milder pH value of an automatic dishwasher detergent. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and any mixtures thereof will be mentioned herein.

The use of citric acid and / or citrates in these formulations has proved to be particularly advantageous for the cleaning performance and rinsing performance of the formulations described herein. Thus, the automatic dishwasher detergent is preferably characterized in that the automatic dishwasher detergent comprises a salt of citric acid or citric acid.

Aminocarboxylic acids and / or salts thereof are another significant class of phosphate-free builders. A particularly preferred representative of this class is methylglycine diacetic acid (MGDA) or a salt thereof, and glutamine diacetic acid (GLDA) or its salt or ethylenediamine diacetic acid (EDDS) or a salt thereof. The content of these aminocarboxylic acids or salts thereof may be, for example, 0.1 to 30% by weight, preferably 1 to 25% by weight, especially 5 to 20% by weight. Aminocarboxylic acids and their salts can be used with the above-mentioned builders, especially also with phosphate-free builders.

The dishwasher detergent according to the present invention may also comprise a sulfopolymer. The weight percentage of the sulfopolymer in the total weight of the dishwasher detergent according to the invention is preferably from 0.1 to 20% by weight, in particular from 0.5 to 18% by weight, particularly preferably from 1.0 to 15% by weight, in particular from 4 to 14% by weight, Especially 6 to 12% by weight. The sulfopolymer is typically used in the form of an aqueous solution, wherein the aqueous solution typically comprises 20 to 70% by weight, especially 30 to 50% by weight, preferably about 35 to 40% by weight of sulfopolymer.

Preferably, the sulfopolymer used is a copolymer polysulfonate, preferably a hydrophobically modified copolymer polysulfonate.

The copolymer may comprise 2, 3, 4 or more different monomer units. Preferred copolymer polysulfonates include, in addition to the sulfonic acid group-containing monomer (s), at least one monomer from the group of unsaturated carboxylic acids.

Particularly preferably, an unsaturated carboxylic acid of the formula R ¹ (R ² ) C═C (R ³ ) COOH is used as the unsaturated carboxylic acid (s), wherein R ¹ to R ³ independently of one another are -H , -CH ₃ , a linear or branched saturated alkyl functional group having 2 to 12 carbon atoms, a straight or branched, monounsaturated or polyunsaturated alkenyl residue having 2 to 12 carbon atoms, -NH ₂ as defined above , An alkyl functional group or an alkenyl moiety substituted with -OH or -COOH, or -COOH or -COOR ⁴ , wherein R ⁴ is a saturated or unsaturated, linear or branched hydrocarbon functional group having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acids are unsaturated carboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid,? -Chloroacrylic acid,? -Cyanoacrylic acid, crotonic acid,? -Phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid , Methylene malonic acid, sorbic acid, cinnamic acid, or mixtures thereof. Of course, it is also possible to use unsaturated dicarboxylic acids.

Of the sulfonic acid group-containing monomers, those having the following formulas are preferable,

^{R 5 (R 6) C =} C (R 7) -X-SO 3 H

Wherein R ⁵ to R ⁷ are independently of each other -H, -CH ₃ , a linear or branched saturated alkyl functional group having 2 to 12 carbon atoms, a linear or branched, monounsaturated Or polyunsaturated alkenyl moieties, alkyl functionalities or alkenyl moieties substituted with -NH ₂ , OH or -COOH, or -COOH or COOR ⁴ , wherein R ⁴ is a saturated or unsaturated, a straight chain or branched hydrocarbon functional groups, X is - (CH _{2) n} - (where n = 0 to 4 _{Im), -COO- (CH 2) k} - ( wherein k = 1 to 6, Im), -C (O _{) -NH-C (CH 3)} 2 -, -C (O) -NH-C (CH 3) 2 -CH 2 - and -C (O) -NH-CH ( CH 3) -CH 2 - is selected from Lt; / RTI &gt; represents a spacer group optionally present.

Of these monomers, those of the following formulas are preferred

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

Wherein, R ⁶ and R ⁷ is independently _{-H, -CH 3, -CH 2 CH} 3, -CH 2 CH 2 CH 3 and -CH (CH ₃₎ is selected from _2, X together are - (CH ₂ ) _n - (where n = 0 to 4 _{Im), -COO- (CH 2) k} - ( wherein k = 1 to 6, Im), -C (O) -NH- C (CH 3) 2 -, -C (O) -NH-C (CH 3) 2 -CH 2 - and -C (O) -NH-CH ( CH 3) -CH 2 - represents a group selected from optionally present spacer.

Particularly preferred sulfonic acid group-containing monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2- acrylamido- 2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propanesulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, Amides, and mixtures of the acids described or water-soluble salts thereof.

The sulfonic acid group may be present in the polymer in a fully or partially neutralized form, i. E. In some or all of the sulfonic acid groups, the acid hydrogen atom of the sulfonic acid group may be replaced by a metal ion, preferably an alkali metal ion, especially a sodium ion. The use of a partially or fully neutralized sulfonic acid group-containing copolymer is preferred according to the invention.

The monomer distribution of the copolymer preferably used is preferably 5 to 95% by weight for the copolymer containing only the carboxylic acid group-containing monomer and the sulfonic acid group-containing monomer, and particularly preferably the sulfonic acid group-containing monomer The content of the monomers is 50 to 90% by weight, the content of the carboxylic acid group-containing monomers is 10 to 50% by weight, and the monomers are preferably selected from those described above.

The molar mass of the sulfo copolymer preferably used can be varied to suit the intended purpose of the polymer's properties. A preferred dishwasher detergent is characterized in that the copolymer has a molar mass of 2000 to 200,000 g / mol ^-1 , preferably 4000 to 25,000 g / mol ^-1 , especially 5000 to 15000 g / mol ^-1 .

Dishwasher detergents may also include additional polymers. Suitable groups of polymers include, in particular, polymers which have a cleansing action, for example rinsing polymers and / or polymers acting as emollients.

The polymer preferably used is an alkyl acrylamide / acrylic acid copolymer, an alkyl acrylamide / methacrylic acid copolymer, an alkyl acrylamide / methyl methacrylic acid copolymer, an alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) (Meth) acrylic acid copolymers, alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, alkyl acrylamide / alkyl methacrylate / alkylamino Methacrylate / alkyl methacrylate copolymers, and copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids, and optionally additional ionic or non-ionogenic monomers.

Additional polymers that may be used include acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and alkali and ammonium salts thereof, acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and alkali and ammonium salts thereof, &Lt; / RTI &gt; ethyl ethyl betaine / methacrylate copolymer.

The cationic polymers that may be used include, but are not limited to, quaternized cellulose derivatives, polysiloxanes containing quaternary groups, cationic guar derivatives, polymeric dimethyldiallylammonium salts, and esters of acrylic acid and methacrylic acid and acrylic acid and methacrylic acid and amides , Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylates and -methacrylates, vinylpyrrolidone / methoimidazolinium chloride copolymers, quaternized polyvinylalcohols , Or from the group of polymers described by the INCI names polyquaternium 2, polyquaternium 17, polyquaternium 18, and polyquaternium 27.

The amounts mentioned above for the surfactants and builders described, unless otherwise indicated, generally refer to the amount used when each surfactant or each builder is used alone. It goes without saying that the amount must be adjusted accordingly when a large number of surfactants or builders are used.

The preparation of the present invention preferably contains at least one enzyme preparation or enzyme composition, which contains at least one enzyme. Suitable enzymes include, but are not limited to, proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxydorodacids, and preferably mixtures thereof. These enzymes are, in principle, of natural origin; Advancing from natural molecules, improved variants are available for use in dishwasher detergents and are used in correspondingly preferred ways. The preparation preferably contains the enzyme in an amount of 1 x ^10-6 to 5% by weight based on the active protein. The protein concentration can be determined using known methods, such as the BCA method or the Buret et al. Method.

Proteases are some of the most technically significant enzymes. These cause protein-containing contaminants on the article to degrade and be cleaned. Among these, the subtilisin type protease (subtilase, subtilo peptidase, EC 3.4.21.62) is of particular importance, and it becomes a serine protease due to the catalytically active amino acid. They act as nonspecific endopeptidases and hydrolyse arbitrary acid amide bonds that lie within the peptide or protein. Their pH optimum value is normally apparently in the alkaline range. Subtilase is naturally formed from microorganisms. Of these, subtilisin, which is formed and secreted, in particular by the Bacillus species, will be referred to as the most significant group in the subtilis.

Examples of subtilisin type proteases that are preferably used in detergents or dishwasher detergents include, but are not limited to, subtilisin BPN 'and Carlsberg, protease PB92, subtilisin 147 and 309, Bacillus lentus, In particular, proteases from Bacillus lentus DSM 5483, subtilisin DY, and thermostatic enzymes (which can be classified as subtilases but can not be classified as subtilisin in a narrower sense), proteinases K, And proteases TW3 and TW7, and variants of the described proteases with modified amino acid sequences relative to the starting protease. For example, proteases are intentionally or randomly modified using methods known from the prior art and thus optimized for use in detergents and dishwasher detergents. These include point mutagenesis, deletion, or insertion mutagenesis with other protein or protein fragments or fusion. Suitably optimized variants are known for most proteases known from the prior art.

Examples of amylases which can be used are Bacillus licheniformis, B. amyloliquefaciens and B. stearothermophilus, Aspergillus niger and Aspergillus niger, Alpha -amylase from A. oryzae, and the development of the above-mentioned amylases improved for use in dishwasher detergents. For this purpose, the cyclodextrin glucanotransferase (CGTase) from α-amylase and B. agaradherens (DSM 9948) from Bacillus sp. A 7-7 (DSM 12368) will be highlighted .

In addition, lipases or cutinases can be used to generate the over-acid from suitable precursors in the system, as well as for their triglyceride-liberation activity. These include, for example, lipases originally obtained from Humicola lanuginosa (Thermomyces lanuginosus) or lipases which have been further developed, in particular lipases containing amino acid substitutions of D96L .

In addition, enzymes combined under the term hemicellulase can be used. They can be used in the form of, for example, mannanase, xanthine lyase, pectin lyase (= pectinase), pectin esterase, pectate lyase, xyloglucanase (= xylanase) .

In order to improve the bleaching action, an oxidoreductase such as an oxidase, an oxidase, a catalase, a peroxidase such as a haloperoxidase, a chloroperoxidase, a bromoperoxidase, a lignin peroxidase, a glucose peroxy A polyglycerin or a manganese peroxidase, a dioxygenase or a lacquer (phenol oxidase, polyphenol oxidase) may be used. Advantageously, it is advantageous to interact with the enzyme (mediator) in order to enhance the activity of certain oxydorodimic agents (enhancers), or to ensure electron flux when there is a large difference in the redox potential of the oxidant and contaminants An organic compound, particularly preferably an aromatic compound, is further added.

In particular, during storage, the enzyme can be protected against damage, e. G., Inactivation, denaturation or disruption due to, for example, physical effects, oxidation or proteolytic cleavage. Inhibiting protein degradation is particularly preferred in the case of microbial production of proteins and / or enzymes, particularly where the agent comprises a protease. Dishwasher detergents may include stabilizers for this purpose; The provision of such agents is a preferred embodiment of the present invention.

Proteases and amylases with cleansing action are generally provided in the form of stabilized, storable and transportable preparations, rather than in the form of pure proteins. These pre-formulated preparations can be concentrated and / or stabilized to the extent possible, for example in the case of solid preparations obtained by granulation, extrusion or freeze-drying, or in particular in the case of liquid or gel-like preparations, A solution of the enzyme mixed with a topical agent or other adjuvant.

Alternatively, the enzyme can be used for both solid and liquid packaging formats, for example by spray drying or extruding an enzyme solution, preferably with a natural polymer, or in the form of capsules, for example enzymes surrounded by solidifying gels , Or the core-shell type, wherein the enzyme-containing core is coated with a protective layer that is impermeable to water, air and / or chemicals. Additional active ingredients such as stabilizers, emulsifiers, pigments, bleaches or dyes may additionally be applied to the overlapped layers. Such capsules are applied in a manner known per se, for example using stirring or roll granulation, or in a fluidized bed process. Such granules are advantageously low-dispersible, for example by application of polymer film formers, and storage stability due to coating.

It is also possible to blend two or more enzymes together so that the individual granules have multiple enzyme activities.

As is apparent from the comments, the enzyme protein forms only a portion of the total weight of the conventional enzyme preparation. The protease and amylase preparations preferably used contain 0.1 to 40% by weight, preferably 0.2 to 30% by weight, particularly preferably 0.4 to 20% by weight, in particular 0.8 to 10% by weight, enzyme proteins. In particular, dishwasher detergents comprising 0.1 to 12 wt%, preferably 0.2 to 10 wt%, especially 0.5 to 8 wt% enzyme preparations, based on the total weight of the dishwasher detergent, are preferred.

The compositions described herein may also comprise an enzyme stabilizing agent. One group of stabilizers is the group of reversible protease inhibitors. Often, in particular derivatives with aromatic groups, such as benzoamidine hydrochloride, borax, benzoyl peroxide, benzoyl peroxide, benzoyl peroxide, benzoyl peroxide and benzoyl peroxide, including ortho, meta- or para-substituted phenylboronic acids, especially 4-formylphenylboronic acid, , Boric acid, boronic acid or its salts or esters are used for this purpose. Peptide aldehydes, oligopeptides with reduced C-termini, especially those formed from 2 to 50 monomers, are used for this purpose. Peptide reversible protease inhibitors include obomucoid and leupeptin. Specific reversible peptide inhibitors and specific peptide inhibitors for protease subtilisin and fusion proteins formed from proteases are also suitable for this purpose.

Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and propanolamine and mixtures thereof, _C12 or lower aliphatic carboxylic acids such as succinic acid, other dicarboxylic acids or salts of the mentioned acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Other enzyme stabilizers are known to those skilled in the art from the prior art.

Bleach is a substance with cleaning action. Of the compounds which function as bleach and produce H ₂ O ₂ in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Additional usable bleaching agents include, for example, peroxypyrophosphate, citrate perhydrate, and peracids or peracids that produce H ₂ O ₂ , such as perbenzoate, peroxophthalate, diperazelaic acid, phthaloimino Peracid, or dipododecanedioic acid. Any additional inorganic or organic peroxy bleach known to those skilled in the art from the prior art can also be used. Percarbonates, and in particular sodium percarbonate, are particularly preferred bleaches.

In various embodiments, the dishwasher detergent comprises from 1 to 35% by weight, preferably from 2.5 to 30% by weight, particularly preferably from 3.5 to 20% by weight, especially from 5 to 15% by weight of bleaching agent, preferably sodium percarbonate . &Lt; / RTI &gt;

In various embodiments of the present invention, the automatic dishwasher detergent further comprises at least one bleaching activator. And compounds which produce, under hydrolysis conditions, aliphatic peroxycarboxylic acids, preferably having from 1 to 10 carbon atoms, especially from 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid, as bleaching activators . Among all bleaching activators known to those skilled in the art from the prior art, polyarylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl- (DADHT), acylated glycoluril, especially tetraacetyl glycoluril (TAGU), N-acylimide, in particular N-nonanoylsuccinimide (NOSI), Especially preferred are hydrogenated phenolsulfonates, in particular n-nonanoyl or iso-nonanoyloxybenzenesulfonate (n- or iso-NOBS). It is also possible to use a combination of conventional bleach activators. TAED is a very particularly preferred bleaching activator, especially in combination with percarbonate bleach, preferably sodium percarbonate.

These bleaching activators are in each case preferably not more than 10% by weight, in particular 0.1 to 8% by weight, in particular 2 to 8% by weight, particularly preferably 2 to 6% by weight, based on the total weight of the preparation It is used in quantities.

Generally, the pH value of the dishwasher detergent can be set using a conventional pH adjusting agent, wherein the pH value is selected according to the intended use purpose. In various embodiments, the pH value is in the range of 5.5 to 10.5, preferably 5.5 to 9.5, more preferably in the range of 7 to 9, in particular in the range of 7 to 7.5. Acids and / or alkalis, preferably alkalis, are used for pH adjustment. Succinic acid is especially an organic acid such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid, and gluconic acid, or amidosulfonic acid. It is, however, also possible to use inorganic acids, hydrochloric acid, sulfuric acid and nitric acid, or mixtures thereof. Suitable bases are derived from the group of alkali metal and alkaline earth metal hydroxides and carbonates, especially alkali metal hydroxides, of which potassium hydroxide, especially sodium hydroxide, is preferred. However, volatile alkalis in the form of, for example, ammonia and / or alkanolamines, which may contain up to 9 carbon atoms in the molecule, are particularly preferred. The alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamines and mixtures thereof.

In order to set and / or stabilize the pH value, the preparations according to the invention may also comprise one or more buffer substances (INCI buffer) in an amount of usually 0.001 to 5% by weight. At the same time, buffers which are complexing agents or even chelating agents (chelator, INCI chelating agent) are preferred. Particularly preferred buffering agents are citric acid or citrate, especially sodium and potassium citrate, such as trisodium citrate 2H ₂ O and tri-potassium citrate H ₂ O.

Glass corrosion inhibitors prevent the appearance of fog, streaking, and scratches as well as the harshness of the glass surface of automatically cleaned glassware. Preferred glass corrosion inhibitors are derived from the group of magnesium and zinc salts and magnesium and zinc complexes. Within the scope of the invention, the zinc salt content in the dishwasher detergent is particularly 0.1 to 5% by weight, preferably 0.2 to 4% by weight, especially 0.4 to 3% by weight, or is the content of zinc in the oxidized form (Zn ^{2 + Is} in each case 0.01 to 1% by weight, in particular 0.02 to 0.5% by weight, in particular 0.04 to 0.2% by weight, based on the total weight of the glass corrosion inhibitor-containing preparation.

Synthesis products of individual odorous substance compounds such as esters, ethers, aldehydes, ketones, alcohols, and hydrocarbon types can be used as perfume oils or fragrances within the scope of the present invention. However, mixtures of different odorants are preferably used, which together produce attractive odor notes. Such perfume oils may also contain a mixture of natural odorous substances, such as those available from plant sources such as pine, citrus, jasmine, coriander, rose, or ylang ylang oil.

Preservatives may also be present in the formulation. Suitable preservatives include, for example, alcohols, aldehydes, antimicrobial acids and / or salts thereof, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, , Benzamidine, isothiazole and its derivatives such as isothiazoline and isothiazolinone, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidine, antimicrobial amphoteric compounds, quinoline, 1,2 Dibromo-2,4-dicyanobutane, iodo-2-propynyl butylcarbamate, iodine, iodophore, and peroxide. Preferred antimicrobial active ingredients are preferably ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid , Thymol, 2-benzyl-4-chlorophenol, 2,2'-methylene-bis- (6-bromo-4-chlorophenol), 2,4,4'- trichloro-2'- N, N '- (10-decanediyl-1-pyridinyl-4-ylidene) -bis- (1 N, N'-bis- (4-chlorophenyl) -3,12-diimino-2,4,11,13-tetraazatetradecane diimide amide, an antimicrobial quaternary Surface-active compounds, and guanidines. However, particularly preferred preservatives are selected from the group consisting of salicylic acid, quaternary surfactants, especially benzalkonium chloride and isothiazole, and derivatives thereof such as isothiazoline and isothiazolinone.

In general, the automatic dishwasher detergents described herein can be formulated in a variety of ways. The formulations may be presented as a solid or liquid presentation form or as a combination of solid and liquid presentation forms. Suitable solid dosage forms are, in particular, powders, granules, extrudates, compressed bodies, in particular tablets. The liquid presentation form based on water and / or organic solvent may be in the form of a gel, in a thick form. The formulations may be formulated in the form of single-phase or multi-phase products. The individual phases of the multi-phase formulation may have the same or different states of aggregation.

Dishwasher detergents may also be present in the form of shaped bodies. In order to facilitate the decomposition of these preformed shaped bodies, it is possible to incorporate the disintegration auxiliaries known as tablet disintegrants into these preparations to shorten the disintegration time. A tablet disintegrating or disintegrating accelerator is understood to mean an adjuvant which ensures rapid degradation of the tablet in water or other medium, and rapid release of the active ingredient. The disintegration aid is preferably used in an amount of 0.5 to 10% by weight, preferably 3 to 7% by weight, in particular 4 to 6% by weight, based on the total weight of the formulation comprising the disintegration aid in each case.

The automatic dishwasher detergent described herein is preferably premixed as an administration unit. These dosing units preferably comprise a substance having the required amount of cleansing action in one cleaning cycle. A preferred dosage unit has a weight of 12 to 30 g, preferably 14 to 26 g, in particular 16 to 22 g. The volume of the above-mentioned dosage unit and its three-dimensional shape are particularly preferably selected to ensure dosability of the premixed unit through the administration chamber of the dishwasher. Therefore, the volume of the administration unit is preferably 10 to 35 ml, especially 12 to 30 mole.

Automatic dishwasher detergents, especially pre-made dosage units, particularly preferably comprise a water-soluble packaging material.

The water-soluble packaging material is preferably formed of a water-soluble film material selected from the group consisting of a polymer or a mixture of polymers. The packaging material may be formed of one layer of water-soluble film material, or two or more layers. The water-soluble film material of the first layer and the water-soluble film material of the further layer may be the same or different if such are present. Particularly preferred is a film that can be packaged, e.g., a tube or cushion, by bonding and / or sealing after loading the agent onto the film.

The aqueous packaging may include one or more chambers. The formulation, if present, may be present in one or more chambers of the aqueous packaging. The amount of preparation preferably corresponds to the total dose, or half dose, required for a single wash operation.

The water-soluble packaging material preferably comprises polyvinyl alcohol or polyvinyl alcohol copolymer. Water-soluble packaging materials comprising polyvinyl alcohol or polyvinyl alcohol copolymers exhibit good stability and sufficiently high water solubility, especially cold water solubility.

Suitable water-soluble films for preparing water-soluble packaging materials preferably have a viscosity in the range of 10,000 to 1,000,000 gmol " ¹ , preferably 20,000 to 500,000 gmol" ¹ , particularly preferably 30,000 to 100,000 gmol " ¹ , particularly 40,000 to 80,000 gmol" ¹ Of a polyvinyl alcohol or a polyvinyl alcohol copolymer.

Polyvinyl alcohol is typically prepared by hydrolysis of polyvinyl acetate, since direct synthesis routes are not possible. The same applies to polyvinyl alcohol copolymers correspondingly prepared from a polyvinyl acetate copolymer. At least one layer of the water-soluble packaging material comprises polyvinyl alcohol having a degree of hydrolysis of 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, in particular 82 to 88 mol% .

Also, polymers selected from the group consisting of (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acids, or mixtures of such polymers, Lt; RTI ID = 0.0 &gt; polyvinylalcohol-containing &lt; / RTI &gt; A further preferred polymer is a polylactic acid.

In addition to vinyl alcohol, preferred polyvinyl alcohol copolymers include dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, itaconic acid being preferred.

Likewise, preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, ethylenically unsaturated carboxylic acids, salts thereof, or esters thereof. In addition to vinyl alcohol, such polyvinyl alcohol copolymers particularly preferably comprise acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.

The film material may preferably contain further additives. For example, the film material may contain a plasticizer such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol, or mixtures thereof. Examples of further additives include mold release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, anti-blocking agents, non-sticking agents or mixtures thereof.

A water-soluble film suitable for use in the aqueous packaging of the aqueous packaging according to the present invention is a film marketed by MonoSol LLC, for example under the names M8630, C8400 or M8900. Other suitable films include films by the name Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH, or films by Kuraray Lt; RTI ID = 0.0 &gt; VF-HP &lt; / RTI &gt; Exemplary formulations of formulations according to the present invention include both phosphate-containing dishwasher detergents and phosphate-free dishwasher detergents. Exemplary formulations in which the metal complexes described herein can be used in specified amounts as additional components are as follows:

Table 1: Phosphate-containing solid dishwasher detergent formulations Tab:

Table 2: Phosphate-free solid dishwasher detergent formulation Tab:

Preferably, 17-20 g of tablets are prepared, wherein 20 g tablets are preferred.

The present invention also relates to the corresponding uses of an automatic dishwasher detergent according to the present invention. The present invention also relates to a dishwashing method, particularly an automatic dishwashing method, using the dishwasher detergent according to the present invention. Thus, the present application also relates to a method of cleaning dishes in a dishwasher, which dispenses the formulation according to the invention into the interior of the dishwasher, before the main washing cycle is started, or during the course of the main washing cycle, while running the dishwashing program . The dispensing or introduction of the formulation according to the invention into the interior of the dishwasher can be done manually, but preferably the formulation is dispensed inside the dishwasher by the dosing chamber.

Embodiments described in the context of the formulation according to the invention can be readily applied to the method and use according to the invention, and vice versa.

<Examples>

Example 1 Synthesis of N-mono-dodecylcyclenes

1,4,7,10-tetraazacyclodecane (1 g, 5.80 mmol) and triethylamine (0.24 mL, 1.74 mmol) were dissolved in 20 mL freshly distilled chloroform. 1-Bromododecane (0.35 mL, 1.45 mmol) was added in small portions to the solution, and the reaction solution was stirred under reflux for 15 hours. The reaction solution was then cooled to room temperature and washed three times with 7 mL NaOH solution (1 M) each time. The organic phase was washed three times with 10 mL of distilled water each time, dried over magnesium sulfate, filtered and the solvent was removed under reduced pressure. The product, N-mono-dodecylcyclen, was obtained as a colorless oil (0.49 g, 1.44 mmol; yield 99%).

Similar to this C ₁₂ cyclene, additional cyclene, such as C ₈ cyclene or C ₁₆ cyclene, was synthesized using the corresponding bromoalkane.

Example 2 Synthesis of Zinc Complex of N-mono-dodecylcyclenes

N-Mono-dodecylcyclen (0.5 g, 1.47 mmol) was dissolved in 10 mL of distilled water and heated to 65 [deg.] C. Zinc sulfate (422 mg, 1.47 mmol) dissolved in 4 mL of distilled water was slowly added dropwise to the milky white solution. The clear, colorless reaction solution was stirred at 65 &lt; 0 &gt; C for 20 h, then hot-filtered and cooled to room temperature. The cooled solution was freeze-dried to give the zinc complex of N-mono-dodecylcyclen (0.51 g, 1.02 mmol, yield 70%).

Similarly, in addition to C ₁₂ cyclylene zinc, additional zinc complex C ₈ cyclylene inks and C ₁₆ cyclylene inks were also prepared.

The described cyclene compounds are shown below along with their formulas:

C8 Zincylene

C12 Cyclylene Zinc

C16 Cyclylene Zinc

Example 3 Synthesis of Copper Complexes of N-mono-dodecylcyclenes

N-Mono-dodecylcyclen (0.49 g, 1.44 mmol) was dissolved in 10 mL of distilled water and heated to 65 [deg.] C. Copper (II) sulfate (230 mg, 1.44 mmol) dissolved in 4 mL of distilled water was slowly added dropwise to the milky white solution. The clear blue reaction solution was stirred at 65 &lt; 0 &gt; C for 20 hours, then hot-filtered and cooled to room temperature. The cooled solution was freeze-dried to obtain a copper complex of N-mono-dodecylcyclen (0.71 g, 1.42 mmol, yield 99%).

Example 4: Cleaning performance

In addition to the phosphate-free basic recipes according to Table 2, the following additional formulations were formulated:

Table 3: Phosphate-containing dishwasher detergent tablets

Table 4: Phosphate-free liquid formulations in pouches

The cleaning performance was determined using a 50 ° C program in a Miele dishwasher. Water hardness 21 ° dH. For this purpose, 20 g of the phosphate-containing solid recipe (Tab) shown in Table 3 was used in combination with 0.1 g of C ₁₂ cyclylene zinc (E1), or 20 g of the phosphate-free liquid recipe (Pouch) was used in combination with 0.1 g of the copper complex (E2) from Example 3. In a comparative experiment, 0.1 g of zinc sulfate heptahydrate (V3), 0.1 g of copper (II) sulfate (V4), or 0.1 g of N-mono-dodecylcyclen (V2) was added to 20 g of the dishwasher detergent recipe , Or the recipe was used without any additives (V1).

After completing the wash cycle, the tableware was visually inspected based on a rating of 1-10. The higher the value, the better the cleaning performance. Compared to the comparative recipe, it was clear that the recipe according to the invention exhibited improved cleaning performance against burned crembrillate contaminants (Table 2).

Table 5: Cleaning performance

In a further experiment, 0.1 g of one of the zinc complexes, C ₈ cyclylene zinc, C ₁₂ cyclylene zinc and C ₁₆ cyclylene zinc, shown in Example 2, was added to 20 g recipe (phosphate-free Tab ) &Lt; / RTI &gt; (E3 to E5). The washing performance was again determined using a 50 ° program (water hardness 21 ° dH) in a Millet household dishwasher. As before, the tableware was visually inspected based on a rating of 1 to 10 after the wash cycle. The higher the value, the better the cleaning performance.

Table 6

It is clear that E3 results in improved cleaning performance for tea (Assam), ground beef (130 DEG C), egg yolk, spaghetti, starch, and crembrillery contaminants compared to reference products V4 and E4 and E5 Respectively. The cleaning performance decreased from C ₈ cyclylene Zn through C ₁₂ cyclylene Zn to C ₁₆ cycloylene Zn, that is, the longer the alkyl chain of the cyclene, the poorer the performance. In addition, E3 was better than the reference for each tested contaminant type.

Claims (14)

Dishwasher detergents, in particular automatic dishwasher detergents, comprising 0.001 to 10.0% by weight, in particular 0.01 to 1.0% by weight, based on the total weight of the dishwasher detergent, of at least one metal complex of the formula (I)
(I)
M ^{n +} L (A ^m- ) _{n / m}
In this formula,
M is a metal cation selected from Groups 2 to 15 of the Periodic Table of the Elements;
A is an optional anion;
n and m are integers selected from 1 to 6;
L is a neutral ligand of formula < RTI ID = 0.0 >
&Lt;

In this formula,
Each X is independently O or NR;
Each R is independently selected from H, unsubstituted or substituted, linear or branched C _1-20 alkyl, unsubstituted or substituted, linear or branched C _1-20 heteroalkyl, unsubstituted or substituted, linear or branched C _{2 -20} alkenyl, unsubstituted or substituted, linear or branched C _2-20 alkenyl heteroaryl, and unsubstituted or substituted, linear or are independently selected from branched C _2-20 alkynyl. Dishwasher detergents, in particular automatic dishwasher detergents, comprising 0.001 to 10.0% by weight, in particular 0.01 to 1.0% by weight, based on the total weight of the dishwasher detergent, of at least one metal complex of the formula (I)
(I)
M ^{n +} L (A ^m- ) _{n / m}
In this formula,
M is a metal cation selected from Groups 2 to 15 of the Periodic Table of the Elements;
A is an optional anion;
n and m are integers selected from 1 to 5;
L is a neutral ligand of formula < RTI ID = 0.0 >
&Lt;

In this formula,
Each X is independently O or NR;
Each R is independently selected from the group consisting of H, - (CH ₂ ) _o -CH ₃ where o is an integer selected from 3 to 13, - (CH ₂ ) _p -COOH and - (CH ₂ ) _p -OH, &Lt; / RTI &gt; The positive electrode according to claim 1 or 2, wherein the metal cation is selected from the group consisting of Cu, Zn, Co, Cr, Ni, Fe, Ru, Rh, cation, more preferably from ^{2 +} Cu, Zn ^{+ 2,} Fe ^{+ 2,} Fe ^{+ 3,} Co ^{+ 2,} Co ^{+ 3,} Mn ^{+ 2,} Mn ^{+ 3} and Bi ^{+ 3,} even more preferably Cu ²⁺ , Zn ^{2 + 3} or Bi ^+, extremely preferably Cu ^{2 +} or Zn ^{+ 2,} and most preferably a dishwasher detergent according to claim ² selected from Zn ^+. The method according to any one of claims 1 to 3, A is ^{F -, Cl -, Br -} , I -, OH -, HSO 3 -, SO 3 2-, SO 4 2-, HSO 4 -, NO ₂ ^- , NO ₃ ^- , PO ₄ ^3- , HPO ₄ ^{2 -} , H ₂ PO ₄ ^- , PF ₆ ^- , ClO ₄ ^- , acetate, citrate, formate, glutarate, lactate, Wherein the detergent is selected from the group consisting of hydrochloride, hydrobromide, nitrate, oxalate, pyruvate, tartrate, methanesulfonate (mesylate), methyl sulfate, tosylate and succinate. Claim 1 to claim 4 according to any one of claims, wherein the R in the general formula II H, unsubstituted or substituted, linear or branched C _1-20 alkyl, unsubstituted or substituted, linear or branched C _{1- 20} &lt; / RTI &gt; heteroalkyl, especially H and linear _C8-18 alkyl. 6. The method according to any one of claims 1 to 5,
(i) at least one X, preferably all X is NR and / or;
(ii) at least one R, preferably 2 to 3, R is H, and at least one R, preferably exactly one, R is a linear _C8-18 alkyl functional group or a _C2-18 hetero alkyl functional group
The dishwasher detergent comprising: 6. The method according to any one of claims 1 to 5,
(i) at least one X, preferably all X is NR and / or;
(ii) is at least one R, and preferably 2 to 3 R is H, at least one R, and preferably exactly one of the _{R - (CH 2) o CH} 3 ( wherein o is selected from 5 to 9 Integer, especially 7)
The dishwasher detergent comprising: 8. The process according to any one of claims 1 to 7, wherein the ligand of formula (II) is selected from the group consisting of N-substituted cyclene (1,4,7,10-tetraazacyclododecane), especially N-mono- Is preferably N-mono-octylcyclen, N-mono-decylcyclene, N-mono-dodecylcyclen, N-mono-tetradecylcyclen or N-mono-hexadecylcyclen, Cu ^{2 +,} Zn ^{2 +,} or a dishwasher detergent, characterized in that Bi ^3+. The process according to claim 8, wherein the ligand of formula (II) is an N-substituted cyclene (1,4,7,10-tetraazacyclododecane), especially N-mono-C _6-10 -alkylcyclene, N-mono-octylcyclen, the metal cation is Zn ^{2 +} , and the anion is SO ₄ ^2- . 10. A composition according to any one of the claims 1 to 9, in combination with at least one of surfactants, especially nonionic and / or anionic surfactants, builders, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, Characterized in that it comprises at least one further component, preferably at least two additional components, selected from the group consisting of an antioxidant, an antioxidant, an antioxidant, an antioxidant, an antioxidant, an antioxidant, . Use of a dishwasher detergent according to any one of claims 1 to 10 in an automatic dishwashing method. A method for cleaning an automatic dishwasher, characterized by using the dishwasher detergent according to any one of claims 1 to 10. Use of a metal complex of formula (I) for improving the cleaning performance of an automatic dishwasher detergent.
(I)
M ^{n +} L (A ^m- ) _{n / m}
In this formula,
M is a metal cation selected from Groups 2 to 15 of the Periodic Table of the Elements;
A is an optional anion;
n and m are integers selected from 1 to 6;
L is a neutral ligand of formula < RTI ID = 0.0 >
&Lt;

In this formula,
Each X is independently O or NR;
Each R is independently selected from H, unsubstituted or substituted, linear or branched C _1-20 alkyl, unsubstituted or substituted, linear or branched C _1-20 heteroalkyl, unsubstituted or substituted, linear or branched C _{2 -20} alkenyl, unsubstituted or substituted, linear or branched C _2-20 alkenyl heteroaryl, and unsubstituted or substituted, linear or are independently selected from branched C _2-20 alkynyl. Use of a metal complex of formula (I) for improving the cleaning performance of an automatic dishwasher detergent.
(I)
M ^{n +} L (A ^m- ) _{n / m}
In this formula,
M is a metal cation selected from Groups 2 to 15 of the Periodic Table of the Elements;
A is an optional anion;
n and m are integers selected from 1 to 5;
L is a neutral ligand of formula < RTI ID = 0.0 >
&Lt;

In this formula,
Each X is independently O or NR;
Each R is independently selected from the group consisting of H, - (CH ₂ ) _o -CH ₃ where o is an integer selected from 3 to 13, - (CH ₂ ) _p -COOH and - (CH ₂ ) _p -OH, &Lt; / RTI &gt;